Visualizing Formation of Intermetallic PdZn in a Palladium/Zinc Oxide Catalyst: Interfacial Fertilization by PdHx

Controllable synthesis of well‐defined supported intermetallic catalysts is desirable because of their unique properties in physical chemistry. To accurately pinpoint the evolution of such materials at an atomic‐scale, especially clarification of the initial state under a particular chemical environment, will facilitate rational design and optimal synthesis of such catalysts. The dynamic formation of a ZnO‐supported PdZn catalyst is presented, whereby detailed analyses of in situ transmission electron microscopy, electron energy‐loss spectroscopy, and in situ X‐ray diffraction are combined to form a nanoscale understanding of PdZn phase transitions under realistic catalytic conditions. Remarkably, introduction of atoms (H and Zn in sequence) into the Pd matrix was initially observed. The resultant PdHx is an intermediate phase in the intermetallic formation process. The evolution of PdHx in the PdZn catalyst initializes at the PdHx/ZnO interfaces, and proceeds along the PdHx ⟨111⟩ direction. A palladium catalyst supported on ZnO is monitored in situ and in chemical environments relevant to catalysis. Structural evolution of PdZn intermetallic metal nanoparticles (NPs), visualized at an atomic scale, reveals the evolution of a PdHx intermediary species at the interface between PdHx and the ZnO support.